Sulfonateds-acylamino



A States SULFON-ATED S-ACYLAMINO-1,9-ISOTHIAZOL- ANTI-IRON ES Paul Biicheler and Albin Peter, Binningen, Switzerland,

assignors to Sandoz A. G., Basel, Switzerland No Drawing. Application September 15, 1955, Serial No. 534,606

Claims priority, application Switzerland September 17, 1954 I 8: Claims. (Cl. 8-55) The present invention relates to valuable acid dyestuffs of the isothiazolanthrone series.

The said dyestuffs of the present invention are obtained by reacting S-acylamino-l,9-isothiazolanthrones, wherein the acyl group is a halogen fatty acid acyl, with alkali metal bisulfites.

In carrying out the-reaction, the acylaminoisothiazolanthrone is heated with an aqueous solution of the alkali metal sulfite at about 100-150 C. until all the waterinsoluble starting material has been consumed. The reaction can be facilitated by the addition of a hydrophilic solvent, such as an alcohol or a phenol, to the reaction mixture. The reaction involves replacement of the halogen atom by the sulfonic acid group.. Anyminor quantity of non-reacting water-insoluble impurities can be removed by filtering th'e' aqueous solution of thereaction product. Any added organic solvent is advantageously removed by steam distillation, prior to the filtration. The resultant dyestuii. is precipitated from the clarified solution by salting out, after which it is filtered off and dried.

As stated, the acyl radical of the starting compounds of the invention are of the halogen fatty acid series. Of primary suitability are the low molecular acyl radicals which contain up to 6 carbon atoms. The halogen atoms are preferably chlorine orbromine atoms; theposition of carrying out of the reaction is concerned. The fatty acid radical present in the starting material can thus be for example the radical of chloracetic acid, l-chloropropionic acid, l-bromopropionic acid, 2-chloropropionic acid, l-bromobutyric acid, l-bromovalerianic acid, l-bromocaproic acid, S-bromoaproic acid, etc.

The new dyestufis of the isothiazolanthrone series thus obtained correspond to the formula lR.--OCHN b wherein R stands for a sulfonated alkyl group. They dissolvein. water, yielding ayellow-colored solution, and dye nitrogenous fibers such as wool, silk and synthetic .polyamides, in yellow shades from such solution. Fibers of, poiyacrylonitrile and mixed polymers thereof are dyed. by

the cupro-ion method in yellow shades of excellent'fastness to washing and tolighn' l The following examples illustrate the invention without, however, being limitative thereof. In these examples, the parts and percentages are by weight, and the temperatures are in degrees centigrade.

Example 1 10 parts of S-chloroacetylamino-1,9-isothiazolanthrone, 30 parts of phenol, 65 parts of aqueous sodium bisulfite solution (40%) and 34 parts of aqueous sodium hydrox- 4'0 substitution is not important, in so far as the successful 2,733,976 Patented Feb. 7,1956

ide, solution (30%) are stirred together at As soon as a test specimen is for the most part soluble in hot, water, the reaction mass is poured into 1000 parts, of water. The solution isheated to 953, filtered hot, and 100 parts of sodium sulfate added. The acid dyestutf, which precipitates on cooling, corresponds to the formula 1 nms-mc-bc-HN it is filtered off with suction, washed with aqueous sodium sulfate solution (10% )l'untilthe filtrate is free from phenol and shows a neutral reaction andisdried. Polyacrylonitrile fibers and fabric can be dyedwith the so-obtained dyestutf by the cnpro-ion method in yellow shades of excellent fastnessto light and to washing.

Example 2 ssesses-. I

fibers and fabrics of wool; silk, or synthetic'polyamides in bright yeliow shades, from. acid solution( Polyacrylonitrile.fibemfandtabriccan be dyed with the said dyestnti by the: cupro ion1 method in yellow shades "of jexcellent fastnesstolight audio-washing. 1

nan-. 3;

anthrone, 30 parts of n-prop'yl'alcohol and 50" parts of neutral aqueous potassiutn sulfite solution (50%) are stirred together at l00"untila test specimen is for the .mostpart soluble :inhqt water; reaction mass is, then heated to 98 in 'SOOJIpai-tsotwatemthejsomtion filtered and the formed acid dyestufi precipitated by the addition of potassium sulfate. 'd estuif; which corresponds to the formula is filtered off with suction, washed with aqueous potassium sulfate solution (8%), and dried. The so-obtained acid dyestuff possesses properties similar to those of the product according to Example 2.

The following table lists additional acid dyestulfs which can be prepared from the enumerated S-halogenacylamino-1,9-isothiazolanthroncs by reaction with alkali metal sulfite after the manner of thepreceding examples:

Shade of Dye lngon Poly- -Halogenacylamino-l,Q-Isothiszolantlnbne.

I v, ucrylonitrile 4 Q 5-(l brcmo)-lsoyalerylsminoyellow.

1,9-isothlazolanthrone Ro -mule of Product:

Ec-nc-"oc-mv mo rio s sir-browsin 1mm 1,9-isothlsm t as Formula'otf'roductr yellow! ams-mo-Iwnw-o c-rm I Example 7 100 parts of a washed skein or hank of polyacrylonitrile (staple fiber) are introduced at 70 into a dyebath which contains parts of a copper screen or netting made of wires of 0.2 'mm. diameter and-which also contains a solution of 1 part of the dyestuii obtained according to Example 1, 1 part of crystalline copper sulfate, 4 parts of concentrated formic acid and 4000 parts of water. The bath is heated to boiling; at the end of an 80-minute boilingperiod, the bath is completely exhausted and thetextile material is dyed a fast yellow.

. tem A fabric of polyacrylonitrile staple fiber is printed with a paste of the following composition: I v

parts of the dyestuff according to Er tample 2,- 50 parts of butyl carbitol; 310 parts of water, 500 parts of crystal gum 1:2,

50 parts of cuprous oxide 1:1, 60 parts of ammonium sulfate 1:2.

1000 parts The print is dried, steamed for 10 minutes at 104 without pressure and for 20 minutes at about and at 1,5 atmospheres pressure, then rinsed well with cold water, soaped at 50-60 with a fatty acid condensate and rinsed again. A full yellow print of very good fastness to light, to washing and to rubbing is obtained.

Having thus disclosed the invention, what is claimed is:

1. An isothiazolanthrone dyestufi of the formula I R-OC-HN wherein R is a sulfonated lower alkyl group.

2. The isothiazolanthrone dyestuff of the formula H0aSHaO-OCHN ii 3. The isothiazolanthrone dyestuif of the formula ll HOaB-HzC-HaC-O C-HN I 4. The isothiazolanthrone dyestutf of the formula HaC--H(IJ-O C-HN o I HOaB '5. The isothiazolanthrone dyestuff of the formula H033 Y 6. The isothiazolanthrone dyestufi of the formula 7;. Hydrophobic fiber material dyed with a product as defined in claim 1.

8. Acrylic polymer dyed with a product as defined in claimtl.

No references cited. 

1. AN ISOTHIAZOLANTHRONE DYESTUFF OF THE FORMULA 